Catalyst management

Catalyst management:

regeneration, reactivation, ex-situ

sulfuration technologies

Gabriella Fogassy

20 March 2013, Sisak

WHERE WE ARE LOCATED?

2

PARIS

La Voulte-sur-Rhône, France

EURECAT IN THE WORLD

Eurecat USPasadena/TX

Eco-RigenGela, Italy

Al-Bilad Catalyst Al-Jubail, Saudi

Arabia

Eurecat IndiaCatalyst Services Jhagadia, Gujarat,

IndiaPetroval USHouston/TX

Tricat USMcAlester/OK

Petroval SASt Romain de Colbosc

Petroval APEurecat Rep. Office

Singapore

Americas Europe Middle East Asia

3

TricatBitterfeld, Germany

Eurecat FranceLa Voulte-sur-Rhône

STANDARDS & VALUES

4

Responsible Care Program

Quality ISO 9001 certification

Environmental ISO 14001 certification

Safety OHSAS* 18001 certification or equivalent

(*Occupational Health and Safety Assessment Series)

Our values:

❑ Innovation

❑ Customer satisfaction

❑ Confidentiality

❑ Ethics

SERVICES, PRODUCTS & TREATMENT

Regeneration /React Sulfiding/Activation

Recycling(metal recovery)

Toll-processing / Manufacturing

Logistics

Reactor Management Services (RMS) / Field services (Petroval )

(Re)sale / Trading

6

UNIT OPERATION/CATALYST LIFE CYCLE

In-situsulfiding

ActivityDp

LoadingFresh Startup RunRegenerationReactivation

Metalreclaim

Unloading

REUSECASCADING

POOLRESALE

7


In-situsulfiding

ActivityDp


Metalreclaim

Unloading

REUSECASCADING

POOLRESALE

8


In-situsulfiding

ActivityDp


Metalreclaim

REUSECASCADING

POOLRESALE

SMARTDUMPCARBODUMP

Ex-situSulfiding:TOTSUCAT

Initial activityDp prediction

Unloading

9


In-situsulfiding

ActivityDp


Metalreclaim

REUSECASCADING

POOLRESALE

SMARTDUMPCARBODUMP



Unloading

REGENERATION TECHNOLOGIES

CONVENTIONALREGENERATION

• Zeolites

• Ni Catalysts

• Pd Catalysts

• CoMo, NiMo, NiW Catalysts

REJUVENATION

• CoMo, NiMo catalysts

DRY REGENERATION

• Zeolites (Confidential)

REGENERATION TECHNOLOGIES

CONVENTIONALREGENERATION

• Zeolites

• Ni Catalysts

• Pd Catalysts

• CoMo, NiMo, NiW Catalysts

REJUVENATION

• CoMo, NiMo catalysts

DRY REGENERATION

• Zeolites (Confidential)

• Ni Catalysts• Pd Catalysts

DEACTIVATION MECHANISMS OF HPC

1. Reversible poisoning:– Carbon: 5-25%– Basic nitrogen (Hydrocracking)From side reactions

2. Structural modifications:– Sintering of metallic particles– Migrations and/or losses of active species– Structure changesFunction of operating conditions

3. Irreversible poisoning:– Metallic contaminants (V, Fe,

As, Hg…)– Silicon, sodium… – Sulfur (Ni…)

Feed composition

Sampling

HPC TREATMENT

Reporting to customer13

Activity testing (lab )

Physico-chemical characterization Activity testing (ind)

Lab regeneration

Physico-chemical characterization

Feed-back to customer

Plant regeneration

Dp prediction

Sampling

HPC TREATMENT




Lab regeneration



Plant regeneration

Dp prediction

Standard

sampling procedure

(for each bed)

15-30 samples are taken and

mixed together and

homogenized before

characterization

Dedicated SAS

sampling procedure

(for each bed)

15-30 samples are taken and

all samples are kept separated

for individual characterization

15

SAMPLING/ANALYSIS

Catalyst is often partly contaminated, partly in good shape

Reactor

MAXIMISE RECOVERY SAS (SAMPLE/ANALYSE/SEGREGATE)

16


SAS: SAMPLE/ANALYSE/SEGREGATE

17❑ Allows to trace metals contamination vs height in reactor.












0

20

40

60

80

100

120

140

160

180

200

Surf

ace

Are

a [m

2/g

]

0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

Van

adiu

m [w

t%]

Reactor height (drum number 1 – N)

Vanadium spec

Must recycle

Can regenerate!


22

❑ Drums/bins should be numbered during unloading!!!

❑ Allows to trace metals contamination vs height in reactor.


23

Case study of 96 tons reactor

❑ Average analyses slightly off-spec

❑ Refiner wanted to send batch for metals recovery.

❑ SAS pointed out contamination was very local

❑ 75% of catalyst could be recovered

❑ 1.3 M$ savings

2 stacked beds – dense load

1 dump pipe (45°)

45°Diameter = 24 cmHeight = 1 m

FROM GRAVITY DUMPING TO SAS

Front view

Side view

FROM GRAVITY DUMPING

Dig outConical shape

SAS

Gravity Unloading

TO SAS

❑ After Gravity dump, SAS can trace back the position of the catalyst in the reactor.

3Q

N° BINSAs

(wt%)V

(wt%)Fe

(wt%)Si

(wt%)Na

(wt%)C spent(wt%)

S spent(wt%)

C lab reg(wt%)

S lab reg(wt%)

SA(m²/g)

2-6-10-12-14 0.25 <0.01 0.07 0.25 0.08 4.8 12.8 0.1 1.5 149

3Q

N° BINSAs

(wt%)V

(wt%)Fe

(wt%)Si

(wt%)Na

(wt%)C spent(wt%)

S spent(wt%)

C lab reg(wt%)

S lab reg(wt%)

SA(m²/g)

42-46-48-50 <0.01 <0.01 0.06 0.03 <0.05 9.0 14.2 0.1 0.8 156

KF757

N° BINSAs

(wt%)V

(wt%)Fe

(wt%)Si

(wt%)Na

(wt%)C spent(wt%)

S spent(wt%)

C lab reg(wt%)

S lab reg(wt%)

SA(m²/g)

Lmm(mm)

%grains < 1.5mm

%grains< 2.0mm

2 0.15 0.00 0.12 0.15 0.09 10.8 13.6 0.1 0.6 141 2.67 6 22

4 0.51 0.00 0.13 0.17 0.07

6 0.24 0.00 0.13 0.17 0.11 9.5 14.3 0.1 0.8 143 3 4 18

8 0.37 0.00 0.14 0.17 0.14

10 0.13 0.00 0.11 0.15 0.08 9.1 13.9 0.1 0.6 142 3.04 2 10

14 0.03 0.00 0.10 0.15 0.08 9.5 13.5 0.1 0.6 142

18 0.02 0.00 0.08 0.16 0.06 10.2 14.2 0.1 0.4 151 2.84 4 15

22 0.01 0.00 0.08 0.15 0.08 10.9 14.1 0.1 0.3 154

26 0.00 0.00 0.07 0.14 0.05 11.0 13.7 0.1 0.4 160 3.31 3 9

30 0.00 0.00 0.06 0.15 0.05 11.0 13.8 0.1 0.3 162

34 0.00 0.00 0.06 0.14 0.04 10.3 14.0 0.1 0.3 152 2.85 4 15

38 0.00 0.00 0.07 0.15 0.05 11.4 14.1 0.1 0.3 162

42 0.00 0.00 0.06 0.16 0.05 12.0 13.4 0.1 0.2 158 3.00 5 14

46 0.00 0.00 0.06 0.15 0.04 12.0 14.0 0.1 0.3 153

50 0.00 0.00 0.06 0.15 0.05 12.0 13.7 0.1 0.3 160 2.66 10 26

Average 0.10 0.00 0.09 0.15 0.07 10.7 13.9 0.1 0.4 152 2.89 5 16

TO SAS

27

Material recycled

Material regenerated/REACTivated

Carbon

Sulfur

Labregenerated

HPCcatalyst

Surface area

BCS (Bulk Crushing Strength)and/or

SCS (Side Crushing Strength)

Average length

PSD (Particle Size Distribution)

Poisons (As, V, Fe, Si, Na, Ni,…)

LAB REGENERATED CATALYST ANALYSIS

Abrasion loss

Sampling

HPC TREATMENT




Lab regeneration



Plant regeneration

Dp prediction

ACTIVITY TEST

❑ Activity recovery is highly dependent on spent catalyst

condition.

❑ Catalyst activity cannot be well quantified from analytical

properties.

Direct activity testing is indispensable to assess reusability.

RVA / RWA (%) measured correlates directly to reactor WABT (°C).

30 30

ACTIVITY VS SURFACE AREA KF757

31No relevant metals contamination on every batch

ACTIVITY TEST

32

MTU OVERWIEV

Capacity: 80 samples/month

Sampler(and degassing section)

HDS – ULSD (10 -100 ppm S)

33

Furnace and 10 reactors in parallel

Sampling

HPC TREATMENT




Lab regeneration



Plant regeneration/sampling

Dp prediction

Sampling

HPC TREATMENT




Lab regeneration




Dp prediction

REGENERATION PARAMETERS OF HPC

36

2 Commercial Hydrotreating catalyst - CoMo on Al2O3

Tailor-made recipes for each individual catalyst

(m2/g) (m2/g)

Carbon

Sulfur

T1 T3T2 T4 T5 T7 T8T6

0

5

10

15

20

Temp (°C)

wt

%

0

50

100

150

200

250

300

SA

(m²/g

)

C (CoMo-1) C (CoMo- 2)

S (CoMo-1) S (CoMo-2)SA (CoMo-1) SA (CoMo-2)

ROTO-LOUVRE

Maximum activity recovery:

❑homogeneous regeneration

❑strict temperature control

❑rapid heat and H2O/SO2 removal

37

REGNERATION FLOW SHEET

38

Regeneration ovenDust

(<1mm) Fines (<1mm)

Gas

Air

Srubber

Spent catalyst

Inerts

3mm (diameter) catalyst

1.3mm (diameter) catalyst❑ Continuous process

❑ High activity recovery (> 95 % SA retention)

❑ Fines guaranteed to be less than 1 wt%

❑ Fine-tuned to each different catalyst

❑ Catalyst evaluation (QC)

PLANT REGENERATION

Fee

din

g &

sie

vin

g

We

igh

tin

g

Siev

ing,

(le

ngt

h g

rad

ing)

,p

acka

gin

g &

we

igh

ing

Re

gen

ere

atio

n

Sampling

HPC TREATMENT




Lab regeneration




Dp prediction

Sampling

HPC TREATMENT




Lab regeneration




Dp prediction

❑ Eurecat has developed unique pressure drop measurement to predict mixed phase delta P in refinery reactor conditions.

Catalyst Performance: Pressure drop

Commercial

DPref (bar)PredictedDP

(bar)

EurecatLab gas phase DPref measurement+ Lab gas phase DP measurement

+ Correlation

❑ Tool has been validated in refinery units (multibed, dense/sock):

Catalyst Performance: Pressure drop

2008 loading scheme = reference 2011 loading scheme

Cat 1Dense loading

Cat 2 Dense loading

Cat 2 Dense loading

Cat 2 Dense loading

Cat 2 Dense loading

Cat 2 Dense loading

Reactor A Reactor B

Cat 3Sock loading

Cat 3Sock loading

Cat 3Sock loading

Cat 3Sock loading

Cat 4Dense loading

Cat 4Dense loading

Reactor A Reactor B

Eurecat laboratory data

Ind

ust

rial

un

it d

ata

PARTICULE SIZE DISTRIBUTION VS PRESSURE DROP

44

0

1

2

3

4

5

6

7

8

9

PS

D (

% v

ol)

Lenght (mm)

Particle Size Distribution (PSD)

Average lenght: 2.4 mmParticles <1.5 mm: 7 wt%Particles <2 mm: 31 wt%

Dp regeneratedcatalyst: 1.22 bar

LENGTH GRADING VS PRESSURE DROP

45

0

1

2

3

4

5

6

7

8

9

PS

D (

% v

ol)

Lenght (mm)

Particle Size Distribution (PSD)

PSD regenerated catalyst (%vol)

PSD after length grading (%vol)

Dp after lenghtgrading: 1.01 bar



Dp regeneratedcatalyst: 1.22 bar

Sampling

HPC TREATMENT




Lab regeneration




Dp prediction

1XXXX/A KF757 3Q Comments: PO number:

1XXXX/B KF767 1.5E FB 66-68 : 40 wt % dust End of treatment: 31/1/2013

Regeneration mass balance

Inerts: (kg) 3528 16 drum(s)

Unregenerated material: 53201 Regenerated catalyst: net: (kg)

net: (kg) KF757\3Q 998 1 BB

57983 68 bins KF767 1.5E 42100 43 BB

Dust: (kg) 1254 7 drum(s) Fines: (kg) 368 11 drum(s)

Regeneration analysis results

1XXXX/B KF767 1.5E Spent: Lab regen: Spec: Regen: Notes: Metals contaminants: (wt%)Notes: Notes:

LOI (wt%): 18.3 - - - As: <0.01 RVA (%): 92 vs fresh

Smoke test: Yes - - - V: <0.01 RWA (%): 98 vs fresh

HC/other volatiles (wt%): 2.9 - - - Fe: 0.2 Dp (bar): 1.01

C (wt%): 14.2 0.1 0.5 0.1 Si: 0.1

S (wt%): 12.0 0.4 0.9 0.5 Na: 0.11

Surface area (m²/g): - 140 137 140 Ni: <0.01

BCS (MPa): - 1.60 1.44 1.58 Regenerated densities: Notes:

Average length (mm): - 3.0 2.8 3.0 CBD (t/m³): 0.843

< 2 mm (%): - 17 20 15 SD (t/m³): 0.784

< 1.5 mm (%): - 6 10 5 PDLD (t/m³): 0.903

Fines (wt%): - - - <0.1 VF (-): 0.325

Additional analysis results can be published via a stock database directly accessible via the Internet

1XXXX/A KF757 3Q Spent: Lab regen: Spec: Regen: Notes: Metals contaminants: (wt%)Notes:

LOI (wt%): 18.3 - - - As: <0.01

Smoke test: Yes - - - V: 0.01

HC/other volatiles (wt%): - - - Fe: 0.12

C (wt%): 14.1 0.1 - 0.1 Si: 0.15

S (wt%): 12.7 0.3 - 0.8 Na: 0.15

Surface area (m²/g): - 176 - 170 Ni: <0.01

BCS (MPa): - - - 1.2 Regenerated densities: Notes:

Average length (mm): - - - 4.8 CBD (t/m³): 0.727

< 2 mm (%): - - - 1 SD (t/m³): 0.676

< 1.5 mm (%): - - - 0 PDLD (t/m³): 0.801

Fines (wt%): - - - <0.1 VF (-): 0.382

EURECAT France

E-mail : [email protected] - Website: www.eurecat.fr

Tel : 33.4.75.62.04.02 - Fax : 33.4.75.85 32.69

ZI Jean-Jaurès - B.P. 45 - 121, Avenue Marie Curie - 07800 LA VOULTE-SUR-RHÔNE - FRANCE

Regen/Lab REACTTM

:

REGENERATIONInitial

screening Final screening

47

Mass balance

Loading parameters

Performance prediction

Catalyst characteristic

Regeneration report

Sampling

HPC TREATMENT




Lab regeneration/reactivation




Dp prediction

Plant reactivation/sampling


REACTIVATION: STARS CATALYST

49E. Brevood, Catalysts Courier 60 (2005) 4.S. Eijsbouts, A.A. Battiston, G.C. van Leerdam, Catal. Today 130 (2008) 361.

STEM-EDX maps of Co (red) and Mo (green)TEM micrograph of CoMo catalyst

Regenerated

Regenerated

REACTivated

REACTivated

Redispersion of the active phase

Experience: more than25 000 tons delivered

EURECAT REACTTM STEPS

RegeneratedSTARS

Catalyst

Fines

REACT

Sampling& analysis

Sieving

Packing &weighting

REACTSTARS

CatalystREACT recipiecannot bedisclosed

Comments: PO number:

1XXXX/A KF767 1.5E

End of treatment:

1/2/2013

Rejuvenation mass balance

Oxidic catalyst: REACT™ catalyst:

net: (kg) net: (kg)

42100 43 BB 50054 43 BB

Rejuvenation analysis results

1XXXX/A KF767 Specs:REACT™: Notes: REACT™ densities: Notes: REACT™ : Notes:

C (wt%): - - CBD (t/m³): 1.039 RVA (%): 95 vs fresh

S (wt%): - - SD (t/m³): 0.966 RWA (%): 101 vs fresh

Surface area (m²/g): - 144 PDLD (t/m³): 1.111 Dp (bar): 1.04

Average length (mm): 2.8 2.85 VF (-): 0.338

< 2 mm (%): 20 19

< 1.5 mm (%): 10 6

Fines (wt%): <1.0 0.2

BCS (MPa): - 1.55

EURECAT France

ZI Jean-Jaurès - B.P. 45 - 121, Avenue Marie Curie - 07800 LA VOULTE-SUR-RHÔNE - FRANCE

Tel : 33.4.75.62.04.02 - Fax : 33.4.75.85 32.69

E-mail : [email protected] - Website: www.eurecat.fr

REACT™ REJUVENATION

51

Mass balance

Loading parameters

Performance prediction

Catalyst characteristic

REACT report

SPECIFIC EURECAT TECHNOLOGIES

Total sulfiding:

• CoMo, NiMo, NiWcatalysts (TOTSUCAT)

Reduction:

• Pd, Pt, PtPd, PtRe, PtSn, Ni, Cu, CuZn...

Selectivation:

• Pd, Pt, PtRe, Ni, Activated carbons

Chlorination:

• Pt, PtRe, PtSn,PtPd

Customized treatments:

• Confidential (treaments for various manufacturers and end-users)

SPECIFIC EURECAT TECHNOLOGIES

Total sulfiding:

• CoMo, NiMo, NiWcatalysts (TOTSUCAT)

Reduction:

• Pd, Pt, PtPd, PtRe, PtSn, Ni, Cu, CuZn...

Selectivation:

• Pd, Pt, PtRe, Ni, Activated carbons

Chlorination:

• Pt, PtRe, PtSn,PtPd

Customized treatments:

• Confidential (treaments for various manufacturers and end-users)

54

In-situsulfiding

ActivityDp



Metalreclaim

SMARTDUMPCARBODUMP



Unloading

REUSECASCADING

POOLRESALE


Temperature (°C)

400

300

200

100

10 20 30 hours +3 days

DMDS

Crackedfeed

Drying step

H2S breakthrough

Secondary Sulfiding

Stop DMDS

•SR Feed + DMDS at 80-150°C•Monitor H2S at outlet •Sulfide at 315-350°C•Sulfiding 3 days of SR feed

Initial Sulfiding

SR Feed

DMDS smell?

Obtain/store SR feed?

DMDS skid failure?

H2S sampling?

Amine unit overload?

Enough hydrogen?

RG compressor failure?

H2S induced corrosion?

Activation procedure

24h coverage?

Correct sulfiding

temperature?

Stripper flooding?

Activation exotherm?

Lose sulfur off the cat?

Catalyst reduction?

Catalyst activity ???

STARTUP WITH IN-SITU SULFIDING

LIQUID PHASE WITH SR FEEDH2S poisoning downstream?

OXYDIC CATALYST

IN-SITUSULFIDING

H2

+ -S-+ heat

H2

+ -S-+ heat

TOTSUCAT™

START-UP

START-UP

IN-SITUACTIVATION

H2

+ heat

START-UP

“PRE-SULFURIZATION”

LOADING

-S-

CATALYST SULFIDING

TOTALLY SULFIDED CATALYST (TOTSUCAT) VS

PRESULPHIDING (ACTICAT, SULFICAT…)

TOTSUCAT™ Presulphiding

Catalyst delivered already at full activity? YES NO

In situ activation required? NO YES

Sulphiding conditions? Optimized for each catalyst

type

Fixed by in situ procedure

Typical start up time 8h 24h+

Need to perform final sulphiding step at 320-350°C

(CoMo/NiMo)?

NOT APPLICABLE YES

Activation exotherm? NOT APPLICABLE YES

Additional H2 required for activation? NOT APPLICABLE YES

Typical H2S level in recycle gas during startup < 500 vppm 1-2 vol%

Need to sample/monitor H2S production in recycle gas? NO YES

Risk of H2S contamination of downstream unit or amine unit

overload?

NO YES

Flexibility during start up (Is it possible to hold the procedure

and resume)?

YES NO

Risk of losing H2S (i.e. catalyst activity) in case of

incident/upset or for once-through unit?

NO YES

Risk of H2S induced corrosion in unit or downstream unit? NO YES

Sour water production? NEGLEGIBLE YES

Need to plan for 72 hours of straight-run feed? YES / NO for TOTSUCAT-CFP YES

Catalyst hazardous goods class UN 3190 / ADR 4.2 UN 3190 / ADR 4.2

Air loading possible? Under certain conditions with

close monitoring(for Air Stab);

OK (for LUBOX)

Under certain conditions

with close monitoring

Packaging UN drums or CHEP bins UN drums or CHEP bins

TOTSUCAT™ Presulphiding

Catalyst delivered already at full activity? YES NO

In situ activation required? NO YES

Sulphiding conditions?Optimized for each

catalyst type

Fixed by in situ

procedure

Typical start up time 8h 24h+

Need to perform final sulphiding step at

320-350°C (CoMo/NiMo)?NOT APPLICABLE YES

Activation exotherm? NOT APPLICABLE YES

Additional H2 required for activation? NOT APPLICABLE YES

Typical H2S level in recycle gas during

startup< 500 vppm 1-2 vol%

TOTSUCAT® BENEFITS

Easy and quick

No DMDS or other sulfiding chemical to handle

No additional H2 needed at startup

No activation exotherm

No need to reach final sulfiding temperature

No recycle gas sampling / H2S monitoring

No impact of H2S on downstream units

Fail-proof: upsets will not damage the catalyst

Maximum catalyst performance

TYPICAL TOTSUCAT® APPLICATIONS

• Downtime cost for in situ sulfiding often outweighs Totsucat cost.

• Totsucat with Amine passivation for Hydrocrackers saves precious startup time.

Critical Path Units

• Some units cannot achieve correct sulfiding temperature: in situ sulfided catalysts will not perform as designed.

Temperature Limited Units

• Reformers and Isom units contain precious metal catalysts that are sensitive to H2S contamination.

Before Sulfur Sensitive Units

• Some units are difficult to sulfide, as there is not enough H2

available at the time of startup.

Hydrogen Limited Units

Over 1200 Totsucat lots treated worldwide: 30 000 tons of catalyst

Hydrotreating

• CoMo, NiMo, NiCoMo

Selective Hydrogenation

• NiMo and CoMo

Pyrolysis Gasoline

• NiMo and CoMo

Hydrocracking

• NiMo and NiW

Lube / Wax Hydrofinishing

• NiMo and CoMo

• NiW

Other…

• Biofuels

• Contaminant traps

• …..

TOTSUCAT® COMMERCIAL EXPERIENCE

TOTSUCAT ® BRANDS

• Naphtha, Kero, FCC gasoline, Tail Gas, Lubes

TOTSUCAT – G

• (Ultra Low Sulfur) DieselTOTSUCAT – D

• Hydrocracking PretreatTOTSUCAT – N

• FCC PretreatTOTSUCAT – E

• HydrocrackingTOTSUCAT – HC

• Light Cycle Oil, Heavy Cycle Oil

• Coker and Visbreaker Naphtha / DieselTOTSUCAT – CFP

Temperature (°C)

400

300

200

100


DMDS

Crackedfeed

Drying step

H2S breakthrough

Secondary Sulfiding

Stop DMDS


Initial Sulfiding

SR Feed

STARTUP WITH IN-SITU SULFIDING

Temperature (°C)


Crackedfeed

DMDS

Drying step

H2S breakthrough

Secondary Sulfiding

Stop DMDS


Initial Sulfiding

SR Feed

SR Feed introduction at low T (80-150°C) Go to Start of Run Temp in only 6-10 h

Straight Runfeed

400

300

200

100

STARTUP WITH TOTSUCAT® G/D/E/N/HC

❑ Startup Liquid phase with SR Feed

ISSUE OF CRACKED FEED

Cracked feed (from Coker, FCC)contains (di)olefins and aromatics

Exposed to freshly sulfidedcatalyst, they polymerise

Gums deposits blockcatalyst pores and active

sites

Leading to a permanent loss in catalytic activity

❑ Catalyst manufacturers recommend a break-in period of at least 3 daysusing straight run feed. Solution: TOTSUCAT CFP

TOTSUCAT® CFP

• TOTSUCAT®-CFP mimics the 3 days break-in period

• Catalytic acidity is reduced no gums formation

• Can inject cracked feed immediately

• Proven in refineries: 60+ references

CFP = Cracked Feed Protection

• lost opportunity in order of ~500 k$

• plus associated logisitics cost.

Example case of 75 tons reactor treating 30% cracked feed

CASE STUDY

Recommendations from Catalyst Supplier:• « In a stressed unit, once the deactivation rate is high, it is nearly

impossible to reduce it. 2-3 % LCO added at the wrong moment is sufficient to double the deactivation rate.

• Therefore, it is critical to have a gentle and possibly somewhat lengthy startup to avoid premature activity loss.

• Run 3 days on virgin oil prior to the introduction of cracked stocks. Longer is better!

• Introduce cracked stocks in a slow, steady, controlled manner.• Do not push the unit in the first two weeks of operation! »

Instead, the refinery appliedTotsucat CFP

CASE STUDY - TOTSUCAT® CFP IN ULSD SERVICE AFTER 90 DAYS

ΔT = 35°F

Normalized to 0.2 wt% S

WA

BT

( F

°)

NORMALIZED TO 0.20 WT% S

Day on stream

CASE STUDY - TOTSUCAT® CFP IN ULSD SERVICE AFTER 320 DAYS

Normalized to 0.2 wt% S

❑Deactivation significantly lower with TOTSUCAT-CFP than with in situ!

ΔT = 35°F

Run length:50+ days

TOTSUCAT ® BRANDS

• Naphtha, Kero, FCC gasoline, Tail Gas, Lubes

TOTSUCAT – G

• (Ultra Low Sulfur) DieselTOTSUCAT – D

• Hydrocracking PretreatTOTSUCAT – N

• FCC PretreatTOTSUCAT – E

• HydrocrackingTOTSUCAT – HC AP

Acidity protection

• Light Cycle Oil, Heavy Cycle Oil

• Coker and Visbreaker Naphtha / DieselTOTSUCAT – CFP

HYDROCRACKING PROCESS: 2 STEPS OF REACTIONS

HDC: ISSUE OF START-UP

❑ Fresh vs steady state catalysts

▪ Zeolite catalyst contains very strong acidic sites: can crack hydrocarbons already around 250°C

▪ In steady state, the strongest acidic sites are essentially covered with N containing compounds (mainly ammonia) cracking temperatures are between 300 and 350°C.

❑ How to go from a fresh to a steady state catalysts?

1. Wait for a long time that N in the feed, transformed by HDN to NH3, slowly saturates the acidic sites

2. Inject during sulfiding procedure NH3 or another N containing compound

3. Use the TOTSUCAT HC-AP

HYDROCRACKER START-UP WITH TOTSUCAT HC-AP

❑ Heating up is very smooth and without

any significant exotherm

❑ Start-up has been performed, according to

expectations: acidity enough passivated,

but not too much

❑ Principle has been approved by UOP

CONCLUSIONS

❑ Catalyst regeneration andreuse allows to drasticallyreduce expense:

❑ TOTSUCAT:

▪ Optimise catalystperformance

▪ Reduce unit downtime

Catalyst end-users: oil refiners & (petro)chemicals companies

Catalyst manufacturers

REGULAR CUSTOMERS

Group

http://www.pcs.com.sg/home

Catalyst end-users: oil refiners & (petro)chemicals companies

Catalyst manufacturers

REGULAR CUSTOMERS

THANK YOU FOR YOU

ATTENTION!

Group

http://www.pcs.com.sg/home

Documents

Catalyst management